JPH0247120A - Graft copolymer having reactivity useful as resin additive and preparation thereof - Google Patents
Graft copolymer having reactivity useful as resin additive and preparation thereofInfo
- Publication number
- JPH0247120A JPH0247120A JP19961588A JP19961588A JPH0247120A JP H0247120 A JPH0247120 A JP H0247120A JP 19961588 A JP19961588 A JP 19961588A JP 19961588 A JP19961588 A JP 19961588A JP H0247120 A JPH0247120 A JP H0247120A
- Authority
- JP
- Japan
- Prior art keywords
- graft copolymer
- weight
- formula
- structural unit
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 81
- 239000011347 resin Substances 0.000 title abstract description 17
- 229920005989 resin Polymers 0.000 title abstract description 17
- 239000000654 additive Substances 0.000 title description 5
- 230000000996 additive effect Effects 0.000 title description 4
- 230000009257 reactivity Effects 0.000 title description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 34
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 9
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 41
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- -1 aliphatic alcohols Chemical class 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical group OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 101100108967 Human herpesvirus 6B (strain Z29) U70 gene Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012213 gelatinous substance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は樹脂添加剤として有用な反応性を有するグラフ
ト共重合体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a reactive graft copolymer useful as a resin additive and a method for producing the same.
グラフト共重合体は、単独重合体やランダム共重合体等
、他の重合体では得られない特性を発現することができ
るため１種々の用途に利用されている０本発明は、樹脂
添加剤として有用な反応性を有するグラフト共重合体で
あって、とりわけ、分子内にエポキシ基と非反応性末端
基でＭ鎖されたポリカプロラクトングラフト鎖を有する
、構造の規制されたグラフト共重合体及びその製造方法
に関するものである。Graft copolymers can exhibit properties that cannot be obtained with other polymers, such as homopolymers and random copolymers, so they are used for a variety of purposes. Graft copolymers having useful reactivity, especially structurally controlled graft copolymers having polycaprolactone graft chains M-chained with epoxy groups and non-reactive end groups in the molecule; This relates to a manufacturing method.
〈従来の技術、その課題〉
従来、グラフト共重合体の製造においては、合成高分子
或は天然高分子に単量体を反応させ、グラフト化させる
方法が採られている。この種の従来法には、既存の高分
子が利用できるという長所がある反面、原料である高分
子が溶媒に溶解し難いものが多いため、反応の困難な場
合が多いという問題がある。またこの種の従来法では、
木質的にグラフト鎖の数或は長さ等の制御が困難である
とともに、グラフト化率が低いため、目的とする構造及
び物性を有するグラフト共重合体を得ることが困難であ
るという問題がある。<Prior art and its problems> Conventionally, in the production of graft copolymers, a method has been adopted in which a synthetic polymer or a natural polymer is reacted with a monomer to form a graft. This type of conventional method has the advantage of being able to use existing polymers, but has the problem that many of the raw material polymers are difficult to dissolve in solvents, making the reaction difficult in many cases. In addition, in this type of conventional method,
Due to the nature of wood, it is difficult to control the number and length of graft chains, and the grafting rate is low, making it difficult to obtain a graft copolymer with the desired structure and physical properties. .
最近、従来のものに比べてより高い分子量の単量体（以
下、マクロモノマーという）を用い、ダラト共重合体を
製造する方法が検討されるようになってきている。この
方法は、予め分子量や構造の制御されたマクロモノマー
を合成しておき、次に該マクロモノマーを他のビニル単
量体と共重合して高分子鎖へ組込むことにより、グラフ
ト共重合体を製造する方法である。Recently, a method of producing a Dalat copolymer using a monomer (hereinafter referred to as macromonomer) having a higher molecular weight than conventional monomers has been studied. In this method, a macromonomer with a controlled molecular weight and structure is synthesized in advance, and then the macromonomer is copolymerized with other vinyl monomers and incorporated into a polymer chain to create a graft copolymer. This is a method of manufacturing.
このようなマクロモノマーを用いるグラフト共重合体の
例として、枝部分にポリエステル鎖を有するグラフト共
重合体が開示されている（特公昭５４−４４０２４、特
開昭６Ｏ−９９１５８）。As an example of a graft copolymer using such a macromonomer, a graft copolymer having a polyester chain in a branch portion has been disclosed (Japanese Patent Publication No. 44024/1989, Japanese Patent Application Laid-Open No. 60-99158).
これらによると、枝部分であるポリエステル鎖を得る方
法として、二塩基酸とグリコールとの重縮合反応、ポリ
カプロラクトンの開環重合、或は酸無水物とアルキレン
オキサイドとの開環重合が例示されている。これらのポ
リエステル鎖の二個の末端基はもともといずれも水酸基
若しくはカルボン酸基であって、これらの末端基の一つ
に各種の反応薬剤を反応させてビニル基を導入すること
によってマクロモノマーを得ており、該マクロモノマー
を他のビニル単量体と共重合してグラフト共重合体を製
造しているのである。According to these, the polycondensation reaction of a dibasic acid and a glycol, the ring-opening polymerization of polycaprolactone, or the ring-opening polymerization of an acid anhydride and an alkylene oxide are exemplified as methods for obtaining a polyester chain, which is a branch part. There is. The two terminal groups of these polyester chains are originally hydroxyl groups or carboxylic acid groups, and macromonomers are obtained by reacting various reactive agents with one of these terminal groups and introducing a vinyl group. The macromonomer is copolymerized with other vinyl monomers to produce a graft copolymer.
ところが、かかる従来法には次のような問題がある。
１）その末端基が水酸基やカルボン酸基となっているマ
クロモノマーを使用するため、構造不明のゲル状物が生
成し易く、構造の規制されたグラフト共重合体を製造し
難い、２）とりわけ、上記のように例示されている方法
でマクロモノマーを得ると、両末端にビニル基の導入さ
れた二官能性マクロモノマーの副生が避けられず、しか
もこれらの二官能性マクロモノマーは精製によって除去
することが極めて困難であるため、結局は該二官能性マ
クロモノマーを共重合反応に関与させることとなって、
その結果、三次元化したゲル状物が顕著に生成してしま
う。However, this conventional method has the following problems.
1) Since a macromonomer whose terminal group is a hydroxyl group or a carboxylic acid group is used, a gel-like substance with an unknown structure is likely to be produced, making it difficult to produce a graft copolymer with a controlled structure.2) Above all, When a macromonomer is obtained by the method exemplified above, the by-product of a bifunctional macromonomer with vinyl groups introduced at both ends is unavoidable, and furthermore, these bifunctional macromonomers cannot be purified by purification. Since it is extremely difficult to remove, the bifunctional macromonomer ends up being involved in the copolymerization reaction,
As a result, a three-dimensional gel-like substance is significantly produced.
そして、このように公知の方法で製造されるグラフト共
重合体は本発明の目的である樹脂添加剤としては種々の
欠点を有する。すなわち、公知の方法で製造されるグラ
フト共重合体は、樹脂に対する良好な分散性が得られず
、とりわけ、該グラフト共重合体をポリエステル樹脂、
ポリカーボネート樹脂、ポリアミド樹脂等の縮合系高分
子の中へ溶融混練すると、前記した水酸基やカルボン酸
基等の末端基の作用によって、樹脂の着色や粘度低下が
起こり、明らかに樹脂を劣化させてしまうのである。Graft copolymers produced by such known methods have various drawbacks when used as resin additives, which is the object of the present invention. That is, graft copolymers produced by known methods do not have good dispersibility in resins.
When melt-kneaded into condensation polymers such as polycarbonate resins and polyamide resins, the resin becomes colored and its viscosity decreases due to the action of the aforementioned terminal groups such as hydroxyl groups and carboxylic acid groups, which clearly deteriorates the resin. It is.
〈発明が解決しようとする課題、その解決手段〉本発明
は、銀型の如き従来の課題を解決する新たなグラフト共
重合体及びその製造方法を提供するものである。<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a new graft copolymer that solves the conventional problems such as silver type, and a method for producing the same.
しかして本発明者らは、上記状況に鑑み、耐熱性が良好
であって、且つポリエステル樹脂、ポリアミド樹脂、ポ
リカーボネート樹脂等の樹脂と溶融混練した際に、これ
らの樹脂の劣化を引き起こすことのないグラフト共重合
体を得るべく鋭意研究した結果、分子内にエポキシ基と
非反応性末端基で封鎖されたポリカプロラクトングラフ
ト鎖を有する、構造の規制されたグラフト共重合体が正
しく好適であり、しかも該グラフト共重合体が工業上有
利に製造し得るものであることを見出し。However, in view of the above circumstances, the present inventors have developed a material that has good heat resistance and does not cause deterioration of resins such as polyester resins, polyamide resins, and polycarbonate resins when melt-kneaded with these resins. As a result of intensive research to obtain a graft copolymer, it was found that a graft copolymer with a controlled structure, which has a polycaprolactone graft chain blocked with an epoxy group and a non-reactive end group in the molecule, is correct and suitable. It was discovered that the graft copolymer can be produced industrially advantageously.
本発明に到達したのである。The present invention has been achieved.
すなわち本発明は、
それぞれ下記の式で示される構成単位工及び構成単位■
並びに構成単位ＩＩＩを含有し、構成単位工が全体の８
０〜２０重量％、構成単位■が全体の１０〜７９重量％
、構成単位ＩＩＩが全体の１〜２０重量％であり、且つ
構成単位工＋構成単位ＩＩ十構成単位ＩＩＩが全体の６
０重量％以上であることを骨子とするグラフト共重合体
と、示されるビニル単量体を１〜２０重量％及び活性水
素基を有しないその他のビニル単量体を０〜４０重量％
の比率で、重合開始剤の存在下に共重合させることを骨
子とするグラフト共重合体の製造方法とに係る。In other words, the present invention provides a structural unit work and a structural unit shown by the following formulas, respectively.
It also contains structural unit III, and the structural unit work is 8 of the total.
0 to 20% by weight, structural unit ■ is 10 to 79% by weight of the whole
, the constituent unit III is 1 to 20% by weight of the whole, and the constituent unit work + the constituent unit II + the constituent unit III is 6% of the whole
A graft copolymer whose main content is 0% by weight or more, 1 to 20% by weight of the vinyl monomer shown, and 0 to 40% by weight of other vinyl monomers that do not have active hydrogen groups.
The invention relates to a method for producing a graft copolymer, the gist of which is copolymerization in the presence of a polymerization initiator at a ratio of .
構成単位ｍ ： ＋ＣＨ２−（ニド
非反応性末端基を有する下記の一般式Ａで示されるビニ
ル重合性ポリカプロラクトン誘導体を８０〜２０重量％
、下記の一般式Ｂで示されるビニル単量体を１０〜７９
重量％、下記の一般式Ｃで畷
一般式Ｂ ： ＣＨ２−Ｃ−Ｒ’
［各式を通じて、Ｒ１、Ｒ３、Ｒ５； Ｈ又はＣＨ３Ｒ
２；炭素数１〜１８の脂肪族若しくは脂環族炭化水素基
又は−ＥＧｓＨ２＊０）ｒＲ６（ここに、Ｒ６；炭素数
１〜１８の炭化水素基、ｍ；２又は３、ｒ；１〜５）
” ； ０６！’１５、ＣＯＯＣＨ３又はＣ００Ｃ２Ｈ
ｓｘ ； ｃｏｏ又はＣＨ２０
ｎ ； ６〜９０１
本発明のグラフト共重合体において構成単位Ｉの原料と
なる、一般式Ａで示されるビニル重合性ポリカプロラク
トン誘導体（以下、マクロ七ツマ−Ａという）は、−価
アルコールとε−カプロラクトンとの開環付加反応、及
びそれに次ぐα、β−不飽和モノカルボン酸若しくはそ
れらのエステル形成性誘導体を用いるエステル化反応又
はエステル交換反応によって得られる。−価アルコール
とε−カプロラクトンとの開環付加反応は、テトラブト
キシチタネートやジブチル錫ジラウレート等の触媒の存
在下に行なうことができる。Structural unit m: +CH2- (80 to 20% by weight of a vinyl polymerizable polycaprolactone derivative represented by the following general formula A having a nido non-reactive end group)
, the vinyl monomer represented by the following general formula B is 10 to 79
% by weight, with the following general formula C: General formula B: CH2-C-R' [throughout each formula, R1, R3, R5; H or CH3R
2; aliphatic or alicyclic hydrocarbon group having 1 to 18 carbon atoms or -EGsH2*0) rR6 (here, R6; hydrocarbon group having 1 to 18 carbon atoms, m; 2 or 3, r; 1 to 5) ”; 06!'15, COOCH3 or C00C2H
sx ; coo or CH20 n ; 6-901 The vinyl polymerizable polycaprolactone derivative represented by the general formula A (hereinafter referred to as Macro-Natsuma-A), which is the raw material for the structural unit I in the graft copolymer of the present invention, is It is obtained by a ring-opening addition reaction between a -hydric alcohol and ε-caprolactone, followed by an esterification reaction or transesterification reaction using an α,β-unsaturated monocarboxylic acid or an ester-forming derivative thereof. The ring-opening addition reaction between the -hydric alcohol and ε-caprolactone can be carried out in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin dilaurate.
上記−価アルコールの具体例としては、次ぎのようなも
のが挙げられる。Specific examples of the above-mentioned -hydric alcohols include the following.
１）直鎖脂肪族アルコール；メタノール、エタノール、
ｎ−ブタノール、ｎ−オクタノール、オクタデシルアル
コール等
２）分岐脂肪族アルコール；イソプロパツール、２−エ
チルヘキサノール、イソトリデシルアルコール等
３）その他の脂肪族若しくは脂環族アルコール；ベンジ
ルアルコール、シクロヘキサノール等４）以上の１）〜
３）のアルコール類のアルキレンオキサイド付加物；メ
チルセロソルブ、ブチルセロソルブ、エチルカービトー
ル、プチルカービトール等
５）フェノール若しくは炭化水素基で置換されたフェノ
ール類のフルキレンオキサイド付加物；エチレングリコ
ールモノフェニルエーテル、ジエチレングリコールモノ
フェニルエーテル、ポリオキシエチレン（５モル）ノニ
ルフェニルエーテル、エトキシ化−ｐ−フェニルフェノ
ール、エトキシ化−３，５−ジブチルフェノール等であ
る。1) Straight chain aliphatic alcohol; methanol, ethanol,
n-butanol, n-octanol, octadecyl alcohol, etc. 2) Branched aliphatic alcohols; isopropanol, 2-ethylhexanol, isotridecyl alcohol, etc. 3) Other aliphatic or alicyclic alcohols; benzyl alcohol, cyclohexanol, etc. 4) Above 1)~
3) alkylene oxide adducts of alcohols; methyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, etc. 5) fullylene oxide adducts of phenols substituted with phenol or hydrocarbon groups; ethylene glycol monophenyl ether; These include diethylene glycol monophenyl ether, polyoxyethylene (5 mol) nonylphenyl ether, ethoxylated-p-phenylphenol, ethoxylated-3,5-dibutylphenol, and the like.
４）及び５）のフルキレンオキサイド付加物においては
、アルキレンオキサイドとして、エチレンオキサイド又
はプロピレンオキサイドが挙げられ、これらアルキレン
オキサイドの付加モル数は、１〜５モルである。In the fullylene oxide adducts 4) and 5), the alkylene oxide includes ethylene oxide or propylene oxide, and the number of moles of these alkylene oxides added is 1 to 5 moles.
また、前記のα、β−不飽和モノカルポン酸若しくはそ
れらのエステル形成性誘導体の具体例としては、アクリ
ル酸、メタクリル酸、アクリル酸クロライド、メタクリ
ル酸クロライド、アクリル酸メチル、メタクリル酸メチ
ル等が挙げられる。Further, specific examples of the α,β-unsaturated monocarboxylic acids or their ester-forming derivatives include acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, methyl acrylate, methyl methacrylate, etc. .
そしてこれらを用いるエステル化反応又はエステル交換
反応は、ラジカル重合禁止剤と硫酸やｐ−トルエンスル
ホン酸等の酸性触媒との存在下に行なうことができる。The esterification reaction or transesterification reaction using these can be carried out in the presence of a radical polymerization inhibitor and an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid.
かくして得られるマクロモノマーＡの好ましい分子量の
範囲は８００〜ｔｏｏｏｏであり、更に好ましい分子量
の範囲は１ｏｏｏ〜８０００である。The preferable molecular weight range of the macromonomer A thus obtained is 800 to tooo, and the more preferable molecular weight range is 1ooo to 8,000.
本発明のグラフト共重合体において構成単位Ｈの原料と
なる、一般式Ｂで示されるビニル単量体（以下、ビニル
単量体Ｂという）の具体例としてはスチレン、α−メチ
ルスチレン、メチルメタクリレート、メチルアクリレー
ト、エチルメタクリレート、エチルアクリレートが挙げ
られる。これらは、単独で又は混合で使用することがで
きる。Specific examples of the vinyl monomer represented by the general formula B (hereinafter referred to as vinyl monomer B), which is a raw material for the structural unit H in the graft copolymer of the present invention, include styrene, α-methylstyrene, and methyl methacrylate. , methyl acrylate, ethyl methacrylate, and ethyl acrylate. These can be used alone or in mixtures.
本発明のグラフト共重合体において構成単位■の原料と
なる、一般式〇で示されるビニル単量体（以下、ビニル
単量体Ｃという）の具体例としては、グリシジルメタク
リレート、グリシジルアクリレート、アリルグリシジル
エーテルが挙げられる。これらは、単独で又は混合で使
用することができる。Specific examples of the vinyl monomer represented by the general formula (hereinafter referred to as vinyl monomer C), which is a raw material for the structural unit (2) in the graft copolymer of the present invention, include glycidyl methacrylate, glycidyl acrylate, allylglycidyl Ether is an example. These can be used alone or in mixtures.
本発明のグラフト共重合体においては、構成単位工及び
構成単位■並びに構成単位■以外に、その他の構成単位
を含有していてもよい、かかるその他の構成単位の原料
となるビニル単量体（以下、ビニル単量体りという）の
具体例としては、アクリロニトリル、ブチルアクリレー
ト、？−エチルへキシルアクリレート、メトキシエチル
アクリレート、ブチルメタクリレート、２−エチルへキ
シルメタクリレート、メトキシエチルメタクリレート、
酢酸ビニル、メチルビニルエーテル、フェニルビニルエ
ーテル等、水酸基やカルボン酸基の如き活性水素基を有
しないビニル単量体が挙げられるが、これらのなかでも
アクリロニトリルが有利である。In the graft copolymer of the present invention, the vinyl monomer ( Specific examples of vinyl monomers (hereinafter referred to as vinyl monomers) include acrylonitrile, butyl acrylate, -ethylhexyl acrylate, methoxyethyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate,
Examples include vinyl monomers that do not have active hydrogen groups such as hydroxyl groups and carboxylic acid groups, such as vinyl acetate, methyl vinyl ether, and phenyl vinyl ether. Among these, acrylonitrile is advantageous.
本発明のグラフト共重合体を形成する構成単位の各含有
比は、構成単位工／構成単位ＩＩ／構成単位■／その他
の構成単位＝８０〜２０／１０〜７９／ｌ〜２０１０〜
４０（各重量％）の範囲であり、好ましくは、６９〜３
０／３０〜６９／１〜１５１０〜２５（各重量％）の範
囲である。上記の範囲を外れると、製造されるグラフト
共重合体の発揮する機能、例えば分散性の発現が不充分
となる。The content ratio of each of the structural units forming the graft copolymer of the present invention is: structural unit engineering/structural unit II/structural unit ■/other structural units=80-20/10-79/l-2010-
40 (each weight%), preferably 69 to 3
The range is 0/30 to 69/1 to 1510 to 25 (each weight %). If the amount is outside the above range, the function of the produced graft copolymer, such as dispersibility, will be insufficient.
本発明のグラフト共重合体は、前述したように、マクロ
モノマーＡ１ビニル単量体Ｂ、ｔ’ニル単量体Ｃ及び必
要な場合にビニル単量体りを用いて合成される。この合
成に際しては溶液重合、乳化重合又は懸濁重合等の通常
の方法が適用できる。As described above, the graft copolymer of the present invention is synthesized using macromonomer A, vinyl monomer B, t'yl monomer C, and, if necessary, vinyl monomer R. For this synthesis, conventional methods such as solution polymerization, emulsion polymerization or suspension polymerization can be applied.
合成される本発明のグラフト共重合体の分子量は、５０
００以上であることが好ましく、１００００〜１５００
００の範囲であることが更に好ましい。The molecular weight of the graft copolymer of the present invention to be synthesized is 50
00 or more, preferably 10,000 to 1,500
More preferably, it is in the range of 00.
本発明のグラフト共重合体は、樹脂添加剤として極めて
有用である０例えば、互いに非相溶性の二種以上の合成
樹脂を混合する場合に、安定なポリマーブレンドを形成
することができる分散剤として有用である。The graft copolymer of the present invention is extremely useful as a resin additive; for example, as a dispersant that can form a stable polymer blend when two or more synthetic resins that are incompatible with each other are mixed. Useful.
以下、実施例等によって本発明の構成及び効果をより具
体的にするが、本発明が該実施例に限定されるというも
のではない。Hereinafter, the configuration and effects of the present invention will be explained in more detail through examples, but the present invention is not limited to these examples.
〈実施例等〉
以下に例示するように各実施例及び各比較例のグラフト
共重合体を合成し、それらの結果を後記第１表及び第２
表にまとめて示した。<Examples, etc.> Graft copolymers of each example and each comparative example were synthesized as illustrated below, and the results are shown in Tables 1 and 2 below.
They are summarized in the table.
拳実施例１
・・マクロモノマーＡ−１の合成
エチルセロソルブ５０ｇ及びテトラブチルチタネー）１
ｇをフラスコに仕込み、内部を窒素にて置換後、１５０
℃まで加熱した。そして、（−カプロラクトン２２００
ｇを１時間かけて滴下した後、１５０℃にて２時間反応
を続け、カプロラクトン付加物（水酸基価１４ 、４）
を得た。Fist Example 1 Synthesis of macromonomer A-1 (50 g of ethyl cellosolve and tetrabutyl titanate) 1
After charging 150 g into a flask and purging the inside with nitrogen,
Heated to ℃. And (-caprolactone 2200
g was added dropwise over 1 hour, and the reaction was continued at 150°C for 2 hours to form a caprolactone adduct (hydroxyl value 14.4).
I got it.
次いで、上記で得たカプロラクトン付加物２５０ｇ、メ
タクリル酸８．０ｇ、トルエン２５０ｇ、硫酸０．５ｇ
及びハイドロキノン０．１ｇをフラスコに仕込み、８時
間加熱還流して、エステル化反応を行なった。そして、
内容物を６０℃まで冷却した後、炭酸水素ナトリウムに
て硫酸を中和し、中和によって生成した塩を水を加えて
溶解させた。水層とトルエン層とを分離し、トルエン層
を減圧下に、脱水し、脱溶媒して、マクロモノマ−Ａ−
１（酸価０．４、水酸基価１．１、分子量的３９７０）
を得た（分子量はＧＰＣ法によるポリスチレン換算値、
以下同じ）。Next, 250 g of the caprolactone adduct obtained above, 8.0 g of methacrylic acid, 250 g of toluene, and 0.5 g of sulfuric acid.
and 0.1 g of hydroquinone were placed in a flask and heated under reflux for 8 hours to perform an esterification reaction. and,
After the contents were cooled to 60° C., the sulfuric acid was neutralized with sodium hydrogen carbonate, and water was added to dissolve the salt produced by the neutralization. The aqueous layer and toluene layer are separated, and the toluene layer is dehydrated and solvent removed under reduced pressure to produce macromonomer A-
1 (acid value 0.4, hydroxyl value 1.1, molecular weight 3970)
(Molecular weight is polystyrene equivalent value by GPC method,
same as below).
・・グラフト共重合体Ａ−１の合成
上記のマクロモノマーＡ−１を３０ｇ、メチルメタクリ
レートを２０ｇ、グリシジルメタクリレートをｌｏｇ及
びトルエンを９０ｇ、フラスコに仕込み、内部を窒素置
換した後、加熱した。内温か７０℃になったとき、アゾ
ビスイソブチロニトリルの２％トルエン溶液５０１を徐
々に加えて５時間反応を行なった０次いで、反応溶液を
室温にまで冷却し、これをメタノール５００１中に注ぎ
、共重合物を沈殿させた。析出した白色沈殿をメタノー
ル１００ｍ１で３回洗浄した後に、７０℃で真空乾燥し
て、グラフト共重合体Ａ−１を合成した。グラフト共重
合体Ａ−１は、メチルメタクリレート含肚３３重量％、
オキシラン酸素含量２゜０３重量％、分子量的２２００
０であった。...Synthesis of Graft Copolymer A-1 30 g of the above macromonomer A-1, 20 g of methyl methacrylate, log glycidyl methacrylate, and 90 g of toluene were placed in a flask, and the inside was replaced with nitrogen, followed by heating. When the internal temperature reached 70°C, a 2% toluene solution of azobisisobutyronitrile 501 was gradually added and the reaction was carried out for 5 hours.Next, the reaction solution was cooled to room temperature and poured into methanol 5001. to precipitate the copolymer. The precipitated white precipitate was washed three times with 100 ml of methanol and then vacuum dried at 70°C to synthesize graft copolymer A-1. Graft copolymer A-1 contains 33% by weight of methyl methacrylate,
Oxyrane oxygen content 2.03% by weight, molecular weight 2200
It was 0.
・実施例２
・・グラフト共重合体Ａ−２の合成
実ｍｗｉで得たマクロモノマ−Ａ−１を３０ｇ、メチル
メタクリレートを２７ｇ、グリシジルメタクリレートを
３ｇ用い、実施例１と同様の操作を行なってグラフト共
重合体Ａ−２を合成した。- Example 2 - Synthesis of graft copolymer A-2 Using 30 g of macromonomer A-1 obtained in mwi, 27 g of methyl methacrylate, and 3 g of glycidyl methacrylate, grafting was carried out in the same manner as in Example 1. Copolymer A-2 was synthesized.
グラフト共重合体Ａ−２は、メチルメタクリレート含Ｍ
４１重量％６オキシラン醜素含量ｏ、５４ｉｔ％、分子
量的２７０００であった。Graft copolymer A-2 contains methyl methacrylate
The content of oxirane 6-oxirane was 41% by weight, 54it%, and the molecular weight was 27,000.
・実施例３
・・マクロモノマーＡ−３の合成
実施例１と同様の操作によって、ｎ−オクタノール１３
０ｇに（−カプロラクトン２０５２ｇを反応させ、カプ
ロラクトン付加物（水酸基価２６．１）を得た０次いで
、該カプロラクトン付加物にメタクリル酸を反応させて
、マクロモノマーＡ３（酸価０．６、水酸基価１．０、
分子量的２２２０）を得た。・Example 3 ・・Synthesis of macromonomer A-3 By the same operation as in Example 1, n-octanol 13
0 g was reacted with 2052 g of (-caprolactone to obtain a caprolactone adduct (hydroxyl value 26.1).Next, the caprolactone adduct was reacted with methacrylic acid to form macromonomer A3 (acid value 0.6, hydroxyl value 1.0,
A molecular weight of 2220) was obtained.
・・グラフト共重合体Ａ−３の合成
実施例１と同様の操作によって、マクロモノマーＡ−３
を３０ｇ１メチルメタクリレートを２７ｇ、グリシジル
メタクリレートを３ｇ反応させ。...Synthesis of graft copolymer A-3 By the same operation as in Example 1, macromonomer A-3
30 g of 1 methyl methacrylate and 3 g of glycidyl methacrylate were reacted.
グラフト共重合体Ａ−３を合成した。グラフト共重合体
Ａ−３は、メチルメタクリレート含量４７重量％、オキ
シラン酸素含量０．５重量％、分子量的３３０００であ
った。Graft copolymer A-3 was synthesized. Graft copolymer A-3 had a methyl methacrylate content of 47% by weight, an oxirane oxygen content of 0.5% by weight, and a molecular weight of 33,000.
命実施例４
・・マクロモノマーＡ−４の合成
実施例１と同様の操作によって、フェニルカルピトール
４６ｇに（−カプロラクトン２０９０ｇを反応させ、カ
プロラクトン付加物（水酸基価８．９）を得た０次いで
、該カプロラクトン付加物にメタクリル酸を反応させて
、マクロモノマ−Ａ−４（酸価０．３、水酸基価０．７
、分子量的６４００）を得た。Example 4: Synthesis of Macromonomer A-4 In the same manner as in Example 1, 46 g of phenylcarpitol was reacted with 2090 g of (-caprolactone) to obtain a caprolactone adduct (hydroxyl value 8.9). , by reacting the caprolactone adduct with methacrylic acid to obtain macromonomer A-4 (acid value 0.3, hydroxyl value 0.7).
, molecular weight 6400).
・・グラフト共重合体Ａ−４の合成
実施例１と同様の操作によって、マクロモノマーＡ−４
を３０ｇ、スチレンを２０ｇ１グリシジルメタクリレー
トを１０ｇ０ｇ反応、グラフト共重合体Ａ−４を合成し
た。グラフト共重合体Ａ−４は、スチレン含量３５重量
％、オキシラン酸素含量２．１５重量％、分子量的３５
０００であった。... Synthesis of graft copolymer A-4 By the same operation as in Example 1, macromonomer A-4
30 g of styrene, 10 g of glycidyl methacrylate, and 10 g of glycidyl methacrylate were reacted to synthesize graft copolymer A-4. Graft copolymer A-4 had a styrene content of 35% by weight, an oxirane oxygen content of 2.15% by weight, and a molecular weight of 35%.
It was 000.
・実施例５
実施例１と同様の操作によって、マクロモノマーＡ−４
を３０ｇ、スチレンを２７ｇ、アリルグリシジルエーテ
ルを３ｇ反応させ、グラフト共重合体Ａ−５を合成した
。グラフト共重合体Ａ−５は、スチレン含量４２重量％
、オキシランｍ素含量０．７重量％、分子量的２６００
０であった。・Example 5 Macromonomer A-4 was prepared by the same operation as in Example 1.
30 g of styrene, 27 g of styrene, and 3 g of allyl glycidyl ether were reacted to synthesize graft copolymer A-5. Graft copolymer A-5 has a styrene content of 42% by weight.
, oxirane m content 0.7% by weight, molecular weight 2600
It was 0.
・実施例６
・・マクロモノマーＡ−６の合成
実施例１と同様の操作によって、フェノールエチレンオ
キサイド（４モル）付加物９０ｇにε−カブロラクトン
１３３０ｇを反応させ、カブロラクトン付加物（水酸基
価１３ 、３）を得た０次いで、該カプロラクトン付加
物にメタクリル酸を反応させて、マクロモノマ−Ａ−６
（酸価０．５、水酸基価０．６、分子量的４３００）を
得た。・Example 6 Synthesis of macromonomer A-6 By the same operation as in Example 1, 1330 g of ε-cabrolactone was reacted with 90 g of phenol ethylene oxide (4 mol) adduct to form a cabrolactone adduct (hydroxyl value 13, 3 ) was obtained.Next, the caprolactone adduct was reacted with methacrylic acid to obtain macromonomer A-6.
(Acid value 0.5, hydroxyl value 0.6, molecular weight 4300) was obtained.
・・グラフト共重合体Ａ−６の合成
実施例１と同様の操作によって、マクロモノマーＡ−６
を３０ｇ、スチレンを２７ｇ、グリシジルメタクリレー
トを３ｇ反応させ、グラフト共重合体Ａ−６を合成した
。グラフト共重合体Ａ−６はスチレン含量４３重量％、
オキシラン酸素含量０．４８重量％、分子量的２１００
０であった。...Synthesis of graft copolymer A-6 By the same operation as in Example 1, macromonomer A-6
30 g of styrene, 27 g of styrene, and 3 g of glycidyl methacrylate were reacted to synthesize graft copolymer A-6. Graft copolymer A-6 had a styrene content of 43% by weight,
Oxirane oxygen content 0.48% by weight, molecular weight 2100
It was 0.
・実施例７
・・グラフト共重合体Ａ−７の合成
実施例１と同様の操作によって、マクロモノマ−Ａ−１
を２０ｇ、スチレンを２５ｇ、グリシジルメタクリレー
トを５ｇ及びアクリロニトリルをｌｏｇ０ｇ反応、グラ
フト共重合体Ａ−７を合成した。グラフト共重合体Ａ−
７は、スチレン含量４２重量％、アクリロニトリル含量
１６重量％、オキシラン酸素含量０．８９重量％、分子
量的２７０００であった。・Example 7 ・・Synthesis of graft copolymer A-7 Macromonomer A-1 was synthesized by the same operation as in Example 1.
Graft copolymer A-7 was synthesized by reacting 20 g of styrene, 25 g of styrene, 5 g of glycidyl methacrylate, and log 0 g of acrylonitrile. Graft copolymer A-
No. 7 had a styrene content of 42% by weight, an acrylonitrile content of 16% by weight, an oxirane oxygen content of 0.89% by weight, and a molecular weight of 27,000.
・比較例１
・・マクロモノマーＲ−１の合成
ヒドロキシエチルメタクリレート２５ｇ、テトラブチル
チタネート１ｇ及びハイドロキノン０゜２ｇをフラスコ
に仕込み、内部を窒素にて置換後１５０℃まで加熱した
。そして、ε−カプロラクトン７５０ｇを１時間かけて
滴下した後、１５０℃にて２時間反応を続け、マクロモ
ノマ−Ｒ−１（水酸基価１５．２、分子量的３７００）
を得た。- Comparative Example 1 - Synthesis of macromonomer R-1 25 g of hydroxyethyl methacrylate, 1 g of tetrabutyl titanate and 0.2 g of hydroquinone were placed in a flask, the inside of the flask was purged with nitrogen, and then heated to 150°C. Then, 750 g of ε-caprolactone was added dropwise over 1 hour, and the reaction was continued at 150°C for 2 hours to form a macromonomer R-1 (hydroxyl value 15.2, molecular weight 3700).
I got it.
・・グラフト共重合体Ｒ−１の合成
実施例１と同様の操作によって、溶媒としてトルエンを
９０ｇ用い、マクロモノマ−Ｒ−１を３０ｇ、スチレン
を２５ｇ、グリシジルメタクリレートを５ｇ反応させた
０反応の終了時に、ゲル状物の生成が認められた０反応
溶液を室温にまで冷却し、これをメタノール５００ｍ１
中に注ぎ、共重合物を沈殿させた。析出した白色沈殿を
メタノールｌｏｏｍｌで３回洗浄した後、７０℃で真空
乾燥して、グラフト共重合体Ｒ−１を合成した。グラフ
ト共重合体Ｒ−１は、トルエンに対し膨潤するが、不溶
であったため、その分子量測定ができなかった。...Synthesis of Graft Copolymer R-1 By the same procedure as in Example 1, using 90 g of toluene as a solvent, 30 g of macromonomer R-1, 25 g of styrene, and 5 g of glycidyl methacrylate were reacted. 0 End of reaction The reaction solution, in which formation of a gelatinous substance was observed, was cooled to room temperature and mixed with 500ml of methanol.
to precipitate the copolymer. The precipitated white precipitate was washed three times with methanol room, and then vacuum dried at 70°C to synthesize graft copolymer R-1. Graft copolymer R-1 swelled in toluene, but was insoluble, so its molecular weight could not be measured.
・比較例２
・・マクロモノマーＲ−２の合成
無水フタル酸１４８ｇ、無水コハク酸１００ｇ及びエチ
レングリコール１３０ｇをフラスコに仕込み、１５０℃
にて２時間反応させた。そして、反応物を２００℃に昇
温して縮合を行ない、ポリエステル（酸価１７、水酸基
価２０）を得た。Comparative Example 2 Synthesis of Macromonomer R-2 148 g of phthalic anhydride, 100 g of succinic anhydride, and 130 g of ethylene glycol were placed in a flask and heated at 150°C.
The reaction was carried out for 2 hours. Then, the reaction product was heated to 200° C. to perform condensation to obtain a polyester (acid value: 17, hydroxyl value: 20).
次いで、上記ポリエステルを冷却して１６０℃とし、こ
れに無水マレイン酸８ｇを加えて、１時間反応させ、両
末端にカルボキシル基を有するマクロモノマーＲ−２（
酸価３６、平均分子量的３０３０）を得た。Next, the above polyester was cooled to 160°C, 8 g of maleic anhydride was added thereto, and the mixture was reacted for 1 hour to form the macromonomer R-2 (
An acid value of 36 and an average molecular weight of 3030) were obtained.
・・グラフト共重合体Ｒ−２の合成
上記のマクロモノマ−Ｒ−２を１００ｇ、スチレンを７
０ｇ、グリシジルアクリレートをｌｏｇ及びキシレンを
３００ ｇｏ フラスコに仕込み、溶解させた。これを
８０℃にまで加熱し、窒素を導入しつつ、過酸化ベンゾ
イルＩｇを加えて、６時間反応を続けた。そして、内容
物につき、以下実施例１と同様の操作を行なって、グラ
フト共重合体Ｒ−２を合成した。グラフト共重合体Ｒ−
２は、これをトルエンに溶解させたところ、不溶物が認
められたため、その分子量測定を行なわなかった。... Synthesis of graft copolymer R-2 100 g of the above macromonomer R-2, 7 g of styrene
0 g, log glycidyl acrylate and 300 go xylene were charged into a flask and allowed to dissolve. This was heated to 80° C., benzoyl peroxide Ig was added while nitrogen was introduced, and the reaction was continued for 6 hours. Then, the contents were subjected to the same operations as in Example 1 to synthesize graft copolymer R-2. Graft copolymer R-
When No. 2 was dissolved in toluene, insoluble matter was observed, so the molecular weight was not measured.
・比較例３
・・グラフト共重合体Ｒ−３の合成
実施例１と同様の操作によって、マクロモノマーＡ−１
を７ｇ、メチルメタクリレートを５１ｇ、グリシジルメ
タクリレートを２ｇ反応させて、グラフト共重合体Ｒ−
３を合成した。グラフト共重合体Ｒ−３は、メチルメタ
クリレート含量８４重量％、オキシラン酸素含量０．３
９重量％、分子量的３５０００であった。Comparative Example 3 Synthesis of Graft Copolymer R-3 Macromonomer A-1 was synthesized by the same procedure as in Example 1.
, 51 g of methyl methacrylate, and 2 g of glycidyl methacrylate to form a graft copolymer R-
3 was synthesized. Graft copolymer R-3 had a methyl methacrylate content of 84% by weight and an oxirane oxygen content of 0.3.
The content was 9% by weight and the molecular weight was 35,000.
・比較例４
・・マクロモノマーＲ−４の合成
実施例１と同様の操作によって、エチル七ロソルブ９０
ｇにε−カプロラクトン３４２ｇを反応させ、カプロラ
クトン付加物（水酸基価１３１）を得た０次いで、該カ
プロラクトン付加物にメタクリル酸を反応させて、マク
ロモノマ−Ｒ−４を得り、マクロモノマ−Ｒ−４は、分
子量的５００ε−カプロラクトンの平均付加モル数３で
あった。- Comparative Example 4 - Synthesis of macromonomer R-4 By the same operation as in Example 1, ethyl heptarosolve 90
g was reacted with 342 g of ε-caprolactone to obtain a caprolactone adduct (hydroxyl value 131).Next, the caprolactone adduct was reacted with methacrylic acid to obtain macromonomer R-4. The average number of added moles of molecular weight 500ε-caprolactone was 3.
・・グラフト共重合体Ｒ−４の合成
実施例１と同様の操作によって、マクロモノマーＲ−４
を３０ｇ、スチレンを２７ｇ、グリシジルメタクリレー
トを３ｇ反応させて、グラフト共重合体Ｒ−４を合成し
た。グラフト共重合体Ｒ−４は、スチレン含量４８重量
％、オキシラン酸素含量０．５４重量％、分子量的３１
０００であった。...Synthesis of graft copolymer R-4 By the same operation as in Example 1, macromonomer R-4
Graft copolymer R-4 was synthesized by reacting 30 g of styrene, 27 g of styrene, and 3 g of glycidyl methacrylate. Graft copolymer R-4 had a styrene content of 48% by weight, an oxirane oxygen content of 0.54% by weight, and a molecular weight of 31%.
It was 000.
・比較例５
・・グラフト共重合体Ｒ−５の合成
実施例１と同様の操作によって、マクロモノマ−Ａ−１
を２１ｇ、スチレンを２０ｇ、グリシジルメタクリレー
トを２０ｇ０ｇ反応て、グラフト共重合体Ｒ−５を合成
した。グラフト共重合体Ｒ−５は、スチレン含量３２重
量％、オキシラン酸素含量３．３７重量％、分子量的２
１０００であった・
第１表
第２表
［注ニ一般式Ａのｎは平均付加モル数
本１はメチルメタクリレート、本２はスチレン木３はグ
リシジルメタクリレート、木４はアリルグリシジルエー
テル実施例７はビニル単量体りとしてアクリロニトリル
を使用した木５４＊３３．３／４１．７／８．３／１１
１．８ （１８，８はビニル単量体Ｄ）木６は３４／４
２／８／１Ｂ （１Ｂはその他の構成単ω］・樹脂添加
剤としての評価例
ポリカーボネート（奇人化成社製のパンライトＬ−１２
２５）６０ｇ、ポリブチレンテレフタレート（三菱レイ
ヨン社製のタフペット）４０ｇ及び本発明におけるグラ
フト共重合体又は比較のグラフト共重合体を３ｇ、実験
用小型混線機に仕込み、２５０℃で４分間混練した０次
いで、ホットプレス機を用い、厚さ２■のシートを成形
した。Comparative Example 5 Synthesis of Graft Copolymer R-5 Macromonomer A-1 was prepared in the same manner as in Example 1.
21 g of styrene, 20 g of glycidyl methacrylate, and 20 g of glycidyl methacrylate were reacted to synthesize graft copolymer R-5. Graft copolymer R-5 had a styrene content of 32% by weight, an oxirane oxygen content of 3.37% by weight, and a molecular weight of 2.
Table 1 Table 2 [Note 2: n in general formula A is the average number of moles added. 1 is methyl methacrylate, 2 is styrene, 3 is glycidyl methacrylate, 4 is allyl glycidyl ether, and Example 7 is Wood using acrylonitrile as vinyl monomer 54*33.3/41.7/8.3/11
1.8 (18,8 is vinyl monomer D) Wood 6 is 34/4
2/8/1B (1B is the other component ω) Evaluation example as a resin additive Polycarbonate (Panlite L-12 manufactured by Kijin Kasei Co., Ltd.)
25) 60 g of polybutylene terephthalate (Tuffpet manufactured by Mitsubishi Rayon Co., Ltd.) and 3 g of the graft copolymer of the present invention or a comparative graft copolymer were charged into a small experimental mixing machine and kneaded at 250°C for 4 minutes. Next, a sheet having a thickness of 2 cm was formed using a hot press machine.
併せて、グラフト共重合体を無添加のものについても同
様の操作を行ない、シートを成形した（ブランク）。上
記混練時のトルク曲線によって、混線開始からトルク最
大値に到達するまでの時間（第３表中の時間）を測定し
た。また混練した各試料について、オルソクロロフェノ
ール溶液の３５℃における極限粘度を測定し、下記の式
でΔηを算出して評価した。更に各シートについて、着
色程度を肉眼観察し、ポリカーボネートに由来するガラ
ス転移点（第３表中のＴｇ）をＤＳＣにより測定し、併
せて下記の方法により分散状態を評価した。結果を第３
表に示した。尚、混練開始からトルク最大値に到達する
までの時間が短縮され、またポリカーボネートに由来す
るガラス転移点が下がっていることは、それだけ分散性
が改良されていることを示している。At the same time, the same operation was performed on a sheet without the addition of the graft copolymer to form a sheet (blank). The time from the start of mixing until reaching the maximum torque value (time in Table 3) was measured using the torque curve during kneading. Further, for each kneaded sample, the intrinsic viscosity of the orthochlorophenol solution at 35° C. was measured, and Δη was calculated and evaluated using the following formula. Furthermore, for each sheet, the degree of coloring was observed with the naked eye, the glass transition point (Tg in Table 3) derived from the polycarbonate was measured by DSC, and the dispersion state was also evaluated by the following method. 3rd result
Shown in the table. Note that the fact that the time from the start of kneading until reaching the maximum torque value is shortened and the glass transition point derived from polycarbonate is lowered indicates that the dispersibility is improved accordingly.
・・Δηの算出及び評価基準
Δη＝（（η−ηｏ）／ηｏ ）Ｘ１００［ηは試料の
極限粘度
η０はブランクの極限粘度］
Δη≦−４；不可（物性の低下が大きい）＝４くΔη≦
０；可（物性の低下が小さい）ＯくΔη≦５ ；良（
物性、成形性及び樹脂の流動性も良好）
５くΔη ；不可（成形性及び樹脂の流動性が悪い
）
・・分散状態の評価
シートをクロロホルムに室温で５分間浸漬し、表面をエ
ツチング処理した。エツチング処理後のシートについて
、走査型電子ｍ微鏡により、その表面状態を観察し２分
散状態の均質性と分散系の形状及び及びその大きさを調
べた。この場合、均質性については次のように評価した
。すなわち、分散状態がブランクよりも大きく改善され
、微細な状態となって均質に分散している状態のものを
良とし、ブランクと差のないものを不良とした。...Calculation and evaluation criteria for Δη Δη=((η-ηo)/ηo)X100 [η is the intrinsic viscosity of the sample, η0 is the intrinsic viscosity of the blank] Δη≦−4; Not acceptable (significant decrease in physical properties) = 4 Δη≦
0; Fair (small decrease in physical properties); Δη≦5; Good (
Physical properties, moldability, and resin fluidity are also good) 5 Δη ; Not good (poor moldability and resin fluidity) ・Evaluation of the dispersion state The sheet was immersed in chloroform for 5 minutes at room temperature, and the surface was etched. . After the etching process, the surface condition of the sheet was observed using a scanning electron microscope, and the homogeneity of the two dispersion states and the shape and size of the dispersion system were investigated. In this case, homogeneity was evaluated as follows. That is, those in which the dispersion state was greatly improved compared to the blank and were finely dispersed homogeneously were evaluated as good, and those with no difference from the blank were evaluated as defective.
第３表
本９は太さ１〜５１Ｌのネット状、−留り財（〈発明の
効果〉
６表の結果からも明らかなように、以上説明した本発明
には、良好な耐熱性を有し、しかも特に樹脂の劣化を引
き起こすことなく、互いに相溶性の異なる二種以上の樹
脂を混練する場合に該樹脂に対して優れた分散性能を発
揮するという効果がある。Table 3 Book 9 has a net shape with a thickness of 1 to 51 L. Moreover, it has the effect of exhibiting excellent dispersion performance for the resins when two or more resins having different compatibility with each other are kneaded without causing deterioration of the resins.
Claims (1)
単位II並びに構成単位IIIを含有し、構成単位 I が全体
の８０〜２０重量％、構成単位IIが全体の１０〜７９重
量％、構成単位IIIが全体の１〜２０重量％であり、且
つ構成単位 I ＋構成単位II＋構成単位IIIが全体の６０
重量％以上であるグラフト共重合体。 構成単位 I ：▲数式、化学式、表等があります▼ 構成単位II：▲数式、化学式、表等があります▼ 構成単位III：▲数式、化学式、表等があります▼ ［但し、Ｒ＾１、Ｒ＾３、Ｒ＾５；Ｈ又はＣＨ＿３Ｒ＾
２；炭素数１〜１８の脂肪族若しくは脂胞環族炭化水素
基又は▲数式、化学式、表等があります▼ ｛ここに、Ｒ＾６；炭素数１〜１８の炭化水素基、ｍ：
２又は３、ｒ；１〜５｝ Ｒ＾４；Ｃ＿６Ｈ＿５、ＣＯＯＣＨ＿３又はＣＯＯＣ＿
２Ｈ＿５Ｘ；ＣＯＯ又はＣＨ＿２Ｏ ｎ；６〜９０］ ２、構成単位 I が、 ▲数式、化学式、表等があります▼ である請求項１記載のグラフト共重合体。 ３、構成単位IIが、 ▲数式、化学式、表等があります▼ である請求項１又は２記載のグラフト共重合体。 ４、構成単位IIが、 ▲数式、化学式、表等があります▼ である請求項１又は２記載のグラフト共重合体。 ５、構成単位IIIが、 ▲数式、化学式、表等があります▼ である請求項１、２、３又は４記載のグラフト共重合体
。 ６、構成単位 I ＋構成単位II＋構成単位IIIが全体の１
００重量％である請求項５記載のグラフト共重合体。 ７、非反応性末端基を有する下記の一般式Ａで示される
ビニル重合性ポリカプロラクトン誘導体を８０〜２０重
量％、下記の一般式Ｂで示されるビニル単量体を１０〜
７９重量％、下記の一般式Ｃで示されるビニル単量体を
１〜２０重量％及び活性水素基を有しないその他のビニ
ル単量体を０〜４０重量％の比率で、重合開始剤の存在
下に共重合させることを特徴とするグラフト共重合体の
製造方法。 一般式Ａ：▲数式、化学式、表等があります▼ 一般式Ｂ：▲数式、化学式、表等があります▼ 一般式Ｃ：▲数式、化学式、表等があります▼ ［但し、Ｒ＾１ 、Ｒ＾３、Ｒ＾５；Ｈ又はＣＨ＿３Ｒ
＾２；炭素数１〜１８の脂肪族若しくは脂環族炭化水素
基又は▲数式、化学式、表等があります▼ ｛ここに、Ｒ＾６；炭素数１〜１８の炭化水素基、ｍ；
２又は３、ｒ；１〜５｝ Ｒ＾４；Ｃ＿６Ｈ＿５、ＣＯＯＣＨ＿３又はＣＯＯＣ＿
２Ｈ＿５Ｘ；ＣＯＯ又はＣＨ＿２Ｏ ｎ；６〜９０］ ８、一般式Ａが、 ▲数式、化学式、表等があります▼ である請求項７記載のグラフト共重合体の製造方法。 ９、一般式Ｂで示されるビニル単量体がスチレンである
請求項７又は８記載のグラフト共重合体の製造方法。 １０、一般式Ｂで示されるビニル単量体がメチルメタク
リレートである請求項７又は８記載のグラフト共重合体
の製造方法。 １１、一般式Ｃで示されるビニル単量体がグリシジルメ
タクリレートである請求項７、８、９又は１０記載のグ
ラフト共重合体の製造方法。 １２、活性水素基を有しないその他のビニル単量体がア
クリロニトリルである請求項７、８、９、１０又は１１
記載のグラフト共重合体の製造方法。 １３、一般式Ａで示されるビニル重合性ポリカプロラク
トン誘導体を８０〜２０重量％、一般式Ｂで示されるビ
ニル単量体を１０〜７９重量％、一般式Ｃで示されるビ
ニル単量体を１〜２０重量％、且つそれらの合計が１０
０重量％となる比率で共重合させる請求項１１記載のグ
ラフト共重合体の製造方法。[Claims] 1. Contains structural unit I, structural unit II, and structural unit III each represented by the following formula, with structural unit I accounting for 80 to 20% of the total weight, and structural unit II accounting for 10 to 20% of the total weight. 79% by weight, structural unit III accounts for 1 to 20% by weight of the total, and structural unit I + structural unit II + structural unit III accounts for 60% of the total.
% by weight or more of the graft copolymer. Constituent unit I: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Constituent unit II: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Constituent unit III: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [However, R^1, R ^3, R^5; H or CH_3R^
2; Aliphatic or aliphatic cyclic hydrocarbon group having 1 to 18 carbon atoms, or ▲ Numerical formula, chemical formula, table, etc. ▼ {Here, R^6; Hydrocarbon group having 1 to 18 carbon atoms, m:
2 or 3, r; 1 to 5} R^4; C_6H_5, COOCH_3 or COOC_
2H_5X; COO or CH_2O n; 6-90] 2. The graft copolymer according to claim 1, wherein the structural unit I is: 3. The graft copolymer according to claim 1 or 2, wherein the structural unit II is: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4. The graft copolymer according to claim 1 or 2, wherein the structural unit II is ▲A mathematical formula, a chemical formula, a table, etc.▼. 5. The graft copolymer according to claim 1, 2, 3 or 4, wherein the structural unit III is ▲A mathematical formula, a chemical formula, a table, etc.▼. 6. Constituent unit I + constituent unit II + constituent unit III is 1 of the whole
The graft copolymer according to claim 5, which has a content of 0.00% by weight. 7. 80 to 20% by weight of a vinyl polymerizable polycaprolactone derivative represented by the following general formula A having a non-reactive end group, and 10 to 20% by weight of a vinyl monomer represented by the following general formula B.
79% by weight, 1 to 20% by weight of a vinyl monomer represented by the following general formula C, and 0 to 40% by weight of other vinyl monomers having no active hydrogen groups, and the presence of a polymerization initiator. A method for producing a graft copolymer, which comprises copolymerizing a graft copolymer. General formula A: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula B: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula C: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1, R ^3, R^5; H or CH_3R
^2; Aliphatic or alicyclic hydrocarbon group having 1 to 18 carbon atoms, or ▲ Numerical formula, chemical formula, table, etc. ▼ {Here, R^6; Hydrocarbon group having 1 to 18 carbon atoms, m;
2 or 3, r; 1 to 5} R^4; C_6H_5, COOCH_3 or COOC_
2H — 5 9. The method for producing a graft copolymer according to claim 7 or 8, wherein the vinyl monomer represented by general formula B is styrene. 10. The method for producing a graft copolymer according to claim 7 or 8, wherein the vinyl monomer represented by general formula B is methyl methacrylate. 11. The method for producing a graft copolymer according to claim 7, 8, 9 or 10, wherein the vinyl monomer represented by general formula C is glycidyl methacrylate. 12. Claim 7, 8, 9, 10 or 11, wherein the other vinyl monomer having no active hydrogen group is acrylonitrile.
A method for producing the graft copolymer described. 13. 80 to 20% by weight of the vinyl polymerizable polycaprolactone derivative represented by the general formula A, 10 to 79% by weight of the vinyl monomer represented by the general formula B, and 1% of the vinyl monomer represented by the general formula C. ~20% by weight, and their total is 10
12. The method for producing a graft copolymer according to claim 11, wherein the copolymerization is carried out at a ratio of 0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19961588A JP2701151B2 (en) | 1988-08-10 | 1988-08-10 | Reactive graft copolymers useful as resin additives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19961588A JP2701151B2 (en) | 1988-08-10 | 1988-08-10 | Reactive graft copolymers useful as resin additives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0247120A true JPH0247120A (en) | 1990-02-16 |
| JP2701151B2 JP2701151B2 (en) | 1998-01-21 |
Family
ID=16410801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19961588A Expired - Fee Related JP2701151B2 (en) | 1988-08-10 | 1988-08-10 | Reactive graft copolymers useful as resin additives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2701151B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302748A (en) * | 2006-05-09 | 2007-11-22 | Osaka Gas Co Ltd | New biodegradable compatibilizer and resin composition comprising the same |
-
1988
- 1988-08-10 JP JP19961588A patent/JP2701151B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302748A (en) * | 2006-05-09 | 2007-11-22 | Osaka Gas Co Ltd | New biodegradable compatibilizer and resin composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2701151B2 (en) | 1998-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0357036B1 (en) | Preparation method of comb copolymer, acrylic comb copolymer, and impact resistant resin composition | |
| JPH05156172A (en) | Comb copolymer blend | |
| JPH06298921A (en) | Macromonomer and its polymer | |
| KR20030017552A (en) | Blends of Poly[α-Methylenelact(one)(am)] Homo- and Copolymers | |
| JP2842782B2 (en) | Star-shaped block polymer and method for producing the same | |
| KR100365721B1 (en) | Hyperstructure-controlled aliphatic polyester compounds for a plasticizer of polyvinylchloride and polyvinylchloride blend containing the same | |
| KR100848345B1 (en) | Styrene Resin Composition and Process for Producing the Same | |
| CN109153757B (en) | Macromonomer copolymer and process for producing the same | |
| JPH0247120A (en) | Graft copolymer having reactivity useful as resin additive and preparation thereof | |
| JP2882648B2 (en) | Manufacturing method of thermoplastic water-soluble resin | |
| JP2657993B2 (en) | Dispersant for incompatible synthetic resins | |
| JP2657992B2 (en) | Dispersant for incompatible synthetic resin | |
| Ohishi et al. | A novel process for synthesizing polystyrene and polyarylate block copolymers utilizing telechelic polystyrene | |
| JPH06256442A (en) | Production of graft copolymer | |
| EP0421296B1 (en) | Polyvinyl ester macromonomer and its uses | |
| JPH02296833A (en) | Modifier for synthetic resin | |
| JPH0524926B2 (en) | ||
| JP2657994B2 (en) | Graft copolymers useful as unsaturated polyester resin additives | |
| CN109705251A (en) | Microspheroidal ionomer with cross-linked structure and its preparation method and application | |
| JP2701156B2 (en) | Modifier for unsaturated polyester resin | |
| JPH02199153A (en) | Polyether-imide-ester elastomer molding composition | |
| JP3051212B2 (en) | Novel compatibilizer composed of polycaprolactone grafted copolymer | |
| JP3009201B2 (en) | Polymer containing polyvinyl alcohol-based macromonomer unit | |
| JP3426058B2 (en) | Highly unsaturated lactone polymer and method for producing the same | |
| JP2614838B2 (en) | Graft copolymers useful as unsaturated polyester resin additives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |